A summary about our experiences in the introduction of heterogeneous entrainers in azeotropic and extractive batch distillation is presented in this work. Essential advantages of the application of heterogeneous entrainers are showed by rigorous simulation and experimental verification in a bench batch distillation column for separating several azeotropic mixtures such as acetonitrile – water, n hexane – ethyl acetate and chloroform – methanol, commonly found in pharmaceutical industry.